CN1958564A - New technique for synthesizing hydrazinomethyl ester carbonate in high purity - Google Patents
New technique for synthesizing hydrazinomethyl ester carbonate in high purity Download PDFInfo
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- CN1958564A CN1958564A CN 200510116970 CN200510116970A CN1958564A CN 1958564 A CN1958564 A CN 1958564A CN 200510116970 CN200510116970 CN 200510116970 CN 200510116970 A CN200510116970 A CN 200510116970A CN 1958564 A CN1958564 A CN 1958564A
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- hydrazine
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Abstract
This invention relates to a new process for synthesizing high-purity diazanyl methyl carbonate from dimethyl carbonate and hydrazine hydrate. The process utilizes diluent methanol to dilute dimethyl carbonate and hydrazine hydrate before reaction to prevent and reduce local excess phenomenon during the mixing of the reaction system. The method controls the system temperature below 1 deg.C before uniform mixing of dimethyl carbonate and hydrazine hydrate to prevent side reactions, and controls the reaction temperature at 50-55 deg.C after uniform mixing. Besides, the process adopts thin layer chromatography (TLC) technology to monitor the reaction to ensure the reaction is complete and prevent the residue of hydrazine hydrate in the product.
Description
One, technical field
This patent relates to the new synthetic process of hydrazinomethyl ester carbonate, does not especially take place and makes the main reaction that generates hydrazinomethyl ester carbonate carry out under the processing condition completely novel process by methylcarbonate and hydrazine hydrate prepared in reaction hydrazinomethyl ester carbonate in high purity helping side reaction under the effect of thinner.
Two. background technology
Hydrazinomethyl ester carbonate has another name called and is the carbazic acid methyl esters, is the important synthon of organic chemistry in synthetic.Because its diazanyl can react with the compound that contains carbonyl (as aldehydes or ketones), can synthesize and contain C=NNHCOCH
3One compounds of group, for example it is used for important agricultural chemicals and medical synthetic intermediate quinoxaline methylene radical hydrazinomethyl ester carbonate (JP59029675, JP52108928, US4006142, CA982584, AU8612075, ES2007769, MY23083, MY18278, IE44685, SU650504, CS212276, IN138204, IE38724), triazolone intermediate (GB2185983) and hydrazone derivative (InorganicaChimica Acta, Volume 145, and Issue 1,2May 1988, Pages 53-56) etc. synthetic.
Hydrazinomethyl ester carbonate generally all is to react synthetic by methylcarbonate and hydrazine hydrate, and reaction formula is:
But different synthetic technological conditions makes that the mass discrepancy of hydrazinomethyl ester carbonate product is very big.From 1914, the O.Diels reported first was synthesized since the hydrazinomethyl ester carbonate (O.Diels, Ber.Dtsch.Chem.Ges., 1914,47,2183) by methylcarbonate and hydrazine hydrate reaction, and people improve the processing condition of building-up reactions all the time.Nineteen forty-one, E.Merck has reported and the similar synthetic method of O.Diels (DE285800).This method is mixed by equimolar methylcarbonate and hydrazine hydrate, prepared in reaction hydrazinomethyl ester carbonate under the temperature that reaches 70 ℃ that heats up certainly.1985, P.H.Lange, Jr and N.H.Conn in the synthetic patent of carbohydrazide (US 4496761, JP 59048456 and EP 0103400) also reported the synthetic technological condition of the synthetic intermediate hydrazinomethyl ester carbonate of carbohydrazide simultaneously.This patent is that excessive a little methylcarbonate (2.145 moles) is joined in the hydrazine hydrate (2.06 moles).G.D.Madding in 1987 is 1,2, in the synthetic patent of 4-triazolone intermediate (GB 2185983, and GB 2150567, and FR 2555582, JP60132969, NL 8403635), reported the synthetic of hydrazinomethyl ester carbonate.This method is that hydrazine hydrate is joined in the equimolar methylcarbonate, then prepared in reaction hydrazinomethyl ester carbonate under 68 ℃ temperature.2002, patent CN 1337943, US 6465678, EP 1149070, DE 19902960, the contriver LRodefeld of CA 2361423 etc. are artificial solves the problems such as having impurity I, II, remaining hydrazine and product variable color in the hydrazinomethyl ester carbonate product of stating the synthetic method preparation of using, and under 5-10 ℃ temperature, equimolar methylcarbonate and hydrazine hydrate is joined in the methanol solvate simultaneously. then with mixture 50 ℃ of reactions 1 hour down.Underpressure distillation adds toluene after removing methyl alcohol, water, remaining methylcarbonate and hydrazine, then 80 ℃ once more underpressure distillation remove toluene, water, methylcarbonate and hydrazine.Although this method has reduced the partial impurities in the product, still contain 1.2% I in the product, 0.5% II and the hydrazine of 55ppm.In addition, the adding of toluene not only can make the suitability for industrialized production investment of this technology increase and the raising of raw materials for production cost in the product purification process, and, bring such as environmental pollution also can for the industrial production of hydrazinomethyl ester carbonate and endanger stubborn problems such as the workman is healthy because toluene has volatile and deleterious character.
Therefore, still need at present a kind of novel process for preparing hydrazinomethyl ester carbonate in high purity, with the product of this prepared do not contain the problem of impurity I, II, remaining hydrazine, product variable color and in purge process, do not need adding as toluene etc. volatile and deleterious solvent etc.
Three, summary of the invention
In order to overcome the shortcoming that exists in the existing hydrazinomethyl ester carbonate synthesis technique, patent of the present invention provides a kind of novel process for preparing hydrazinomethyl ester carbonate in high purity, this new synthetic process does not only need to add as volatile and deleterious solvents such as toluene, it is little also to have the suitability for industrialized production investment, the low and eco-friendly advantage of production cost.
Analyze in theory from the organic chemistry molecular reaction, we know that impurity I and II are two by products in the hydrazinomethyl ester carbonate building-up reactions system:
Therefore, the key measure of controlling these two by products is to find an appropriate method, makes material carbon dimethyl phthalate molecule and hydrazine molecule in reaction system, under the reaction system energy that is fit to, all is 1 to 1 collision or contact between the reactant molecule.Obviously, if hydrazine hydrate is joined (patent GB2185983 in the methylcarbonate, GB 2150567, FR 2555582, JP 60132969, the method for taking among the NL 8403635), under the reaction energy that is fit to, in adition process, excessive methylcarbonate will inevitably cause the generation of by product I in the system; If methylcarbonate is joined (patent U S4496761, the method for taking among JP59048456 and the EP 0103400) in the hydrazine hydrate, excessive hydrazine hydrate also will inevitably cause the generation of by product II.Although at patent CN 1337943, US 6465678, EP 1149070, DE 19902960, taked among the CA2361423 equimolar methylcarbonate and hydrazine hydrate are joined method in the methanol solvate simultaneously, to a certain degree alleviated the contradiction of excessive methylcarbonate or hydrazine hydrate, but join the moment of methanol solvate at methylcarbonate and hydrazine hydrate, still can enter the place of reaction solution liquid level at drop, the formation of local excessive methylcarbonate and local excessive hydrazine hydrate is arranged, therefore under suitable reaction system energy, can cause the generation of the II of 1.2% I and 0.5%.
Because it is heat release that methylcarbonate and hydrazine hydrate effect generate the reaction of hydrazinomethyl ester carbonate, the carrying out of reaction will cause the temperature of reaction system to raise.We find under study for action when system temperature be when (comprising 5 ℃) more than 5 ℃, add the obvious rising that affiliation causes system temperature in the time of methylcarbonate and hydrazine hydrate, this explanation is that the energy of system enough provides methylcarbonate and hydrazine hydrate to react needed activation energy when (comprising 5 ℃) more than 5 ℃ at system temperature.So although original patented technology has been taked equimolar methylcarbonate and hydrazine hydrate reaction, owing in the adition process of raw material, exist simultaneously in the reaction system: 1) a certain raw material is local superfluous; 2) system (is comprising 5 ℃) more than 5 ℃ and can provide that enough energy make superfluous methylcarbonate and hydrazine hydrate reaction, or superfluous hydrazine hydrate and the needed activation energy of dimethyl carbonate, so caused the generation of by product I and II.In addition, the remnants of hydrazine are because due to the reaction not exclusively in the product.
Patent of the present invention solves the problems of the technologies described above the technical scheme that is adopted: 1. prevent from thinner and reduce material carbon dimethyl phthalate and hydrazine local excessive phenomenon to occur in the process that adds reaction system; Wherein thinner has adopted the solvent of dissolved carbon dimethyl phthalate and hydrazine simultaneously, be preferably methyl alcohol, because methyl alcohol is except the boiling point that has lower (reaction is easy to separate after finishing), outside the advantage of price lower (outside helping reducing production costs), one of by product that methyl alcohol still reacts, thereby can not increase extra component as thinner to reaction system with methyl alcohol, help the purifying of product; The using method of thinner is before material carbon dimethyl phthalate and hydrazine join reaction system, earlier with methyl alcohol respectively with methylcarbonate and hydrazine dilution; Methylcarbonate and hydrazine fully mixed evenly before, the temperature of reaction system is controlled at below 1 ℃, make fully mixed uniform methylcarbonate and hydrazine to react, can prevent the generation of by product I and II so effectively; When methylcarbonate and hydrazine in reaction system mixed evenly after, take suitable way to make that reaction is complete as far as possible; Suitable way is 1) temperature of reaction is controlled at 50-55 ℃; 2) adopt the TLC technology, extract reaction solution the sample analysis, till the raw material hydrazine disappears, can prevent to contain in the product remaining raw material hydrazine like this.
The invention has the advantages that purity height with the hydrazinomethyl ester carbonate product of this new technology preparation, do not contain impurity I, II, remaining hydrazine, do not have a problem of product variable color yet, owing to do not need in the purge process to add as volatile and deleterious solvents such as toluene, so it is little that this new technology also has the suitability for industrialized production investment, the low and eco-friendly advantage of production cost.
Four, embodiment
The present invention describes in further detail in conjunction with the embodiments:
15 milliliters anhydrous methanol is put in the four-hole boiling flask that reflux condensing tube, two dropping funnels and thermometer are housed, the drying tube of Calcium Chloride Powder Anhydrous is housed above the reflux condensing tube.Flask is inserted in the cryosel bath, anhydrous methanol is cooled to below 0 ℃; Add hydrazine and 12 milliliters of solution that anhydrous methanol is formed in the superincumbent dropping funnel, add methylcarbonate and 10 milliliters of solution that anhydrous methanol is formed in another dropping funnel by 7 grams by 5 grams.Then under the stirring of fierceness, from two dropping funnels, accurately drip the methylcarbonate methanol solution of equal volume amounts and hydrazine methanol solution synchronously in flask.In the dropping process, hierarchy of control temperature is below 0 ℃.After methylcarbonate methanol solution and hydrazine methanol solution drip, reaction solution slowly is warmed up to 50～55 ℃, stirring reaction extracted reaction solution sample and carries out the TLC analysis after half hour, (needed 1.5～2 hours) till the raw material hydrazine disappears.Then under 30 ℃, methyl alcohol is removed in underpressure distillation, the solid phase prod vacuum-drying that obtains 2～3 days is to remove the minor amount of water that produces in the dereaction, obtain the carbazic acid methyl esters white crystal product of 6.5 grams, productive rate is 92.8%, fusing point is 72-73 ℃, and purity is greater than 99%, and the product that obtains is placed in room temperature and air did not have red the generation in 10 days.
Claims (4)
1. the new synthetic process of a hydrazinomethyl ester carbonate in high purity, it is characterized in that using thinner to prevent and reduce the material carbon dimethyl phthalate and the local excessive phenomenon of hydrazine appearance in the process that adds reaction system, do not take place and the main reaction that generates hydrazinomethyl ester carbonate is carried out completely under the processing condition, by the novel process of methylcarbonate and hydrazine hydrate prepared in reaction hydrazinomethyl ester carbonate in high purity helping side reaction.
2. the new synthetic process of a kind of hydrazinomethyl ester carbonate in high purity according to claim 1, it is characterized in that thinner selects methyl alcohol for use, the using method of thinner is before material carbon dimethyl phthalate and hydrazine join reaction system, earlier with methyl alcohol respectively with methylcarbonate and hydrazine dilution.
3. the new synthetic process of a kind of hydrazinomethyl ester carbonate in high purity according to claim 1, it is characterized in that helping processing condition that side reaction do not take place and be methylcarbonate methanol solution and hydrazine methanol solution fully mixed evenly before, the temperature of reaction system is controlled at below 1 ℃.
4. the new synthetic process of a kind of hydrazinomethyl ester carbonate in high purity according to claim 1, it is characterized in that helping making the main reaction that generates hydrazinomethyl ester carbonate to carry out completely processing condition is temperature of reaction to be controlled at 50～55 ℃ when methylcarbonate methanol solution and hydrazine methanol solution are fully mixed after even, adopt the TLC technology to monitor reaction process and reaction end accurately, prevent to contain in the product remaining raw material hydrazine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153490A (en) * | 2011-02-16 | 2011-08-17 | 东营柯林维尔化工有限公司 | Synthesis of ethyl hydrozino-formates |
| CN102898328A (en) * | 2012-10-26 | 2013-01-30 | 山东师范大学 | Synthesis method of diethyl azodicarboxylate and intermediate of diethyl azodicarboxylate |
| CN102898327A (en) * | 2012-10-26 | 2013-01-30 | 山东师范大学 | Synthesis method for dimethyl azodicarboxylate and intermediate thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4496761A (en) * | 1982-08-17 | 1985-01-29 | Olin Corporation | Process for making carbohydrazide |
| DE19902960A1 (en) * | 1999-01-26 | 2000-07-27 | Bayer Ag | Production of high-purity methyl carbazate comprises adding hydrazine and dimethyl carbonate simultaneously to solvent, distilling off solvent and low boilers and purifying product |
-
2005
- 2005-11-01 CN CNB2005101169709A patent/CN100408554C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153490A (en) * | 2011-02-16 | 2011-08-17 | 东营柯林维尔化工有限公司 | Synthesis of ethyl hydrozino-formates |
| CN102898328A (en) * | 2012-10-26 | 2013-01-30 | 山东师范大学 | Synthesis method of diethyl azodicarboxylate and intermediate of diethyl azodicarboxylate |
| CN102898327A (en) * | 2012-10-26 | 2013-01-30 | 山东师范大学 | Synthesis method for dimethyl azodicarboxylate and intermediate thereof |
| CN102898328B (en) * | 2012-10-26 | 2014-12-24 | 山东师范大学 | Synthesis method of diethyl azodicarboxylate and intermediate of diethyl azodicarboxylate |
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Granted publication date: 20080806 Termination date: 20161101 |